Enantioselective formal aza-Diels-Alder reactions of enones with cyclic imines catalyzed by primary aminothioureas.

J Am Chem Soc

Department of Chemistry and Chemical Biology, Harvard University, Cambridge, Massachusetts 02138, United States.

Published: February 2013

A highly enantio- and diastereoselective synthesis of indolo- and benzoquinolizidine compounds has been developed through the formal aza-Diels-Alder reaction of enones with cyclic imines. This transformation is catalyzed by a new bifunctional primary aminothiourea that achieves simultaneous activation of both the enone and imine reaction components.

Download full-text PDF

Source
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC3566267PMC
http://dx.doi.org/10.1021/ja310718fDOI Listing

Publication Analysis

Top Keywords

formal aza-diels-alder
8
enones cyclic
8
cyclic imines
8
enantioselective formal
4
aza-diels-alder reactions
4
reactions enones
4
imines catalyzed
4
catalyzed primary
4
primary aminothioureas
4
aminothioureas highly
4

Similar Publications

Enantioselective Cycloaddition of Formed aza-Dienes and Vinyl Diazo Compounds for the Synthesis of Optically Enriched and Diazo Containing Tetrahydropyridazine.

J Org Chem

December 2024

Chemical Synthesis and Pollution Control Key Laboratory of Sichuan Province, College of Chemistry and Chemical Engineering, China West Normal University, Nanchong 637002, China.

A copper catalyzed enantioselective formal aza-Diels-Alder reaction of formed 1,2-diaza-1,3-dienes from α-halohydrazones and vinyl diazo compounds was described. The protocol provides a variety of optically enriched diazo-containing tetrahydropyridazines in moderate yields and with up to excellent enantioselectivities. The present methodologies utilize chiral oxazolines as the chiral ligands for asymmetric catalysis and feature mild reaction conditions, readily available substrates, and broad substrate scope.

View Article and Find Full Text PDF

In the manuscript the application of dearomative formal normal-electron-demand aza-Diels-Alder cycloaddition in the synthesis of tetrahydrofuropyridines is described. The developed approach utilizes aminocatalytic activation of 2-alkyl-3-furfurals that proceeds formation of the dearomatized dienamine intermediate. Initially obtained cycloadducts have been subjected to subsequent transformations providing access to tetrahydrofuropyridines or functionalized cinnamates.

View Article and Find Full Text PDF

A Rapid Aza-Bicycle Synthesis from Dendralenes and Imines.

Org Lett

October 2023

Research School of Chemistry, Australian National University, Canberra, Australian Capital Territory 2601, Australia.

Article Synopsis
  • Researchers have shown that imines can effectively participate in a type of cycloaddition reaction with dendralenes, expanding the capabilities of the Diels-Alder sequence for synthesizing complex polycarbocycles.
  • This method leads to the formation of hexahydro- and octahydro-isoquinoline structures after undergoing a second Diels-Alder reaction with a different dienophile.
  • Computational studies reveal that the reaction mechanism is stepwise and ionic, and provide insight into an unexpected isomerization of a non-reacting carbon-carbon double bond during the first cycloaddition step.
View Article and Find Full Text PDF

In this article, we report a highly regioselective method for the synthesis of new fused pyridine derivatives─2,3-disubstituted quinolines and 1,2-dihydro-3-pyrazolo[3,4-]pyridin-3-one derivatives. The method is based on the reaction of 1,1-diethoxybutane derivatives with aromatic and heterocyclic nucleophiles. The isolated compounds are similar to the products formed as a result of the Debner-Miller reaction.

View Article and Find Full Text PDF

Inversions in the periselectivity of formal aza-Diels-Alder cycloadditions between α-oxoketenes generated by a thermally-induced Wolff rearrangement and 1-azadienes were observed experimentally as a function of the α-oxoketene and the 1-azadiene, as well as the reaction temperature and time. Some unexpected inversion in the diastereoselectivity was observed, too. These variations in selectivities were fully rationalized by computational modeling using density functional theory (DFT) methods.

View Article and Find Full Text PDF

Want AI Summaries of new PubMed Abstracts delivered to your In-box?

Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!